CN85105504A - The method of separating and purifying Ni and Co with solvent extraction process - Google Patents
The method of separating and purifying Ni and Co with solvent extraction process Download PDFInfo
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- CN85105504A CN85105504A CN 85105504 CN85105504A CN85105504A CN 85105504 A CN85105504 A CN 85105504A CN 85105504 CN85105504 CN 85105504 CN 85105504 A CN85105504 A CN 85105504A CN 85105504 A CN85105504 A CN 85105504A
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- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000000638 solvent extraction Methods 0.000 title claims abstract description 5
- 238000000605 extraction Methods 0.000 claims abstract description 68
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000010941 cobalt Substances 0.000 claims abstract description 30
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 30
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000005238 degreasing Methods 0.000 claims abstract description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract 3
- 239000012074 organic phase Substances 0.000 claims description 25
- 239000012071 phase Substances 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000007127 saponification reaction Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005363 electrowinning Methods 0.000 claims description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims 4
- 239000003929 acidic solution Substances 0.000 claims 3
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 19
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- -1 alkyl phosphonic acid Chemical compound 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Electrolytic Production Of Metals (AREA)
Abstract
The method of separating and purifying Ni and Co with solvent extraction process.Present method be with a kind of organic phosphine extraction agent (domestic be called 5709) to the nickeliferous feed liquid of acidity particularly the sulfuric acid selectivity leach solution containing nickel and carry out multi-stage counter current extraction, remove solution metal impurity, the process membrane phase degreasing unit is removed the organism in the raffinate again, obtain the high purity nickel product by the insoluble anode electrode, containing the cobalt feed liquid and can produce the high-purity cobalt product after the back extraction through 5709 extracting and purifyings.
Organic phosphine extraction agent structural formula is
R wherein
1Alkyl for the 6-8 carbon atom; R
2Be 1-first heptyl.
Description
The invention relates to solvent extraction separating nickel and cobalt purification nickel and cobalt method of electrolyte from the solution of nickeliferous and cobalt.
From the nickel solution that contains cobalt and other impurity, to obtain nickel electrolyte, the general employing:
1. the precipitator method: through oxidation, precipitated iron, copper under certain pH value, again through the strong oxidizer oxidation, precipitate cobalt and other impurity.
2. extraction process: English Patent GB2025917A report, the feed liquid that contains cobalt and nickel can obtain by the ore that sulfuric acid to leach contains cobalt and nickel.The iron that stock liquid contains, copper and other impurity before extraction, are removed by methods such as precipitation, filtrations.Remove feed liquid and alkyl phosphonic acid behind the impurity
The alkyl ester MULTI CONTACT, the separating nickel cobalt.The raffinate aqueous sulfuric acid is generally removed organism with activated carbon adsorption, makes the high purity nickel metal with electrolytic method.
The objective of the invention is to a kind of organic phosphine extraction agent, to acid solution containing nickel particularly the solution containing nickel that leaches of sulfuric acid selectivity carry out single extraction, the organism in the solution is removed in the phase-splitting of process film again, just can reach the requirement of the electrolytic solution of No. 1 electrolytic nickel of Ministry of Metallurgical Industry's ministerial standard.The cobalt feed liquid that contains after the back extraction contains cobalt electrolytic solution with said organic phosphine extraction agent extracting and purifying with regard to getting.
Main points of the present invention be with a kind of organic phosphine extraction agent (domestic be called 5709) to the nickeliferous feed liquid of acidity particularly the sulfuric acid selectivity leach solution containing nickel and carry out multi-stage counter current extraction, extraction temperature 35-60 ℃, the pH value 4.0-6.0 of extraction section outlet raffinate, raffinate gets the high purity nickel product by electrowinning with insoluble anode after removing organism through membrane phase degreasing unit.The cobalt feed liquid that contains after the low sour back extraction is passed through organic phosphine extraction agent (5709) extracting and purifying again and just can be obtained containing cobalt electrolytic solution.Organic phosphine extraction agent (5709) is that a kind of alkylphosphines can make the concentration of cobalt in organic phase improve.Load organic phases enters stripping section (2), in (2), through low acid (～1NH
2SO
4) behind the back extraction cobalt, copper, lead, zinc (keep water outlet pH value 2, then above-mentioned metal is can both back extraction complete), pass through peracid (～6NH again
2SO
4) the back extraction impurity iron, temperature is 30-50 ℃.Organic phase after the back extraction enters saponification section (3), uses the 40%(weight concentration) sodium hydroxide solution to organic phase homogeneous phase saponification, multiplexing.Raffinate enters membrane phase degreasing unit (4), removes organism, and the nickel electrolyte after the purification enters electrolyzer (5), obtains meeting No. 1. nickel plates of metallurgical ministerial standard by electrowinning with insoluble anode.Anolyte then returns leaching, realizes closed cycle.Cobalt feed liquid after the low sour back extraction is carried out secondary separation through 5709 extracting and purifying sections (6) and is purified, and can make the high-purity cobalt product.
Embodiment:
Example 1. is a raw material with height ice nickel sulphuric leachate, with the 0.32M5709-sulfonated kerosene is extracted organic phase, pass through five grades extraction, load organic phases is multiplexing after three grades low sour back extractions, secondary reverse-extraction of high acid, continuous homogeneous phase saponification, organic phase round-robin 74 times, raffinate water all can reach the requirement of No. 1 new liquid of electric nickel of production ministerial standard.
The temperature 50-60 of extraction section ℃, the organic phase saponification deg is 30-35%, compares O/A=1: 6, and import feed liquid PH is 6.2, and outlet raffinate PH is 4.5～5.0, and extraction is carried out in the Centrifugical extraction series devices of five φ 20mm.The results are shown in Table one.
Table one
Raffinate is removed organism through membrane phase degreasing unit, and 5709 content obtain No. 1 electric nickel of metallurgical ministerial standard by electrowinning with insoluble anode after dropping to 0.002 grams per liter.Cobalt nickel ratio is 1: 1 in the load organic phases.The direct yield of nickel is greater than 99%, and the direct yield of cobalt is on average greater than 98%.
The temperature of stripping section is more than 30 ℃.Low sour back extraction 1NH
2SO
4, flow than O/A=5: 1.The aqueous phase cobalt concentration reaches the 9-10 grams per liter after the back extraction, and pH value is about 1.5.Cobalt nickel back extraction ratio is all greater than 99%.Reverse-extraction of high acid 6NH
2SO
4, flow than O/A=1: 1.After back extraction in the organic phase iron-holder less than 1 mg/litre.Back extraction equipment adopts titanium system φ 20mm centrifugal extractor.
Add 40% sodium hydroxide solution while stirring in the organic phase, carry out continuous saponification in the canister of synthetic glass, organic phase and lye ratio=100: the 1(volume), temperature is 25 ℃, and saponification deg is about 30%.
Multiplexing 74 times of organic phase, 100 liters of co-processing waters (leach liquor).Organic phase after multiplexing does not change the partition ratio of cobalt nickel, and the infrared spectrum shape is also basic identical, and concerning electric nickel per ton, the organic phase loss is: kerosene: 48.6 liters, and 5709: 1.6 kilograms.
Example 2: electric molten liquid making liquid behind preliminary deironing copper carries out extracting and purifying with 5709-kerosene again.
Nickelous sulfide high-sulfur plate is an anode, and copper coin is a negative electrode, electric molten liquid making, through atmospheric oxidation, in and behind the deironing copper, obtain and the sulfuric acid selectivity leaches the close feed liquid of composition, except that containing the nickel cobalt, also contain impurity such as a little copper, iron, lead, zinc.Extract with 0.35～0.40M5709-sulfonated kerosene, extraction section adopts the pulsed sieve-plate extraction column of the high 4.5m of φ 200mm, and sieve diameter 6mm is equilateral triangle and arranges free cross-section 35%, distance between plates 50mm; Adopt the sinusoidal wave air pulse, amplitude 12.5～15mm, frequency 80-120 time/minute.The organic phase of load is through φ 100mm, and the pulsed sieve-plate extraction column of high 3.0m hangs down acid (～1NH
2SO4) back extraction, enter the polyvinyl chloride apparatus that the oleophylic phase membrane is housed again and carry out reverse-extraction of high acid.In 300 liters enamel still, carry out saponification, multiplexing through the organic phase behind the reverse-extraction of high acid.
The service temperature of extraction is 50-60 ℃, flows than O/A=1: 6～1: 4, and import ph value of aqueous phase 5.9～6.2, raffinate pH value 4.5～5.0, import feed liquid cobalt concentration is 0.35～1.2 grams per liter; 800 liters of water flows/time.The results are shown in Table two
Table two
Nickel is～80 grams per liters in the raffinate, and impurity content reaches produces the new liquid requirement of No. 1 electric nickel of Chinese Ministry of Metallurgical Industry ministerial standard.5709 content are 10～15PPm in the raffinate, through the raffinate behind the membrane phase degreasing unit organic matter removal on the industrial production electrolyzer, do anode with lead and carry out electrowinning with insoluble anode, produce electric nickel No. 1.Comprise general evaporating, emitting, dripping or leaking of liquid or gas, electric nickel per ton consumes 4.7 kilograms of 5709 extraction agents.The direct yield of nickel＞99%, the direct yield of cobalt＞98%, cobalt nickel ratio is 1: 1 in the load organic phases.
Low sour back extraction is carried out at 30 ℃～35 ℃.Stream is than (O/A is 3～4: 1, and strip liquor acidity is 1.0NH
2SO4, nickel cobalt back extraction ratio is all greater than 99%.Electric nickel per ton consumes vitriol oil 0.07M
3
Reverse-extraction of high acid carries out at 35 ℃, and 5 minutes duration of contact, strip liquor acidity is 6NH
2SO
4, after the back extraction in the organic phase iron level drop to＜0.01 grams per liter by 0.02 grams per liter.
Saponification temperature＞15 ℃, every still churning time is 10 minutes, uses 40%(weight) the sodium hydroxide solution saponification, saponification deg is 30%.
The linkage test of semi-industrial scale moves 980 hours altogether, handles water 425M
3, multiplexing 64 times of organic phase.
Containing the cobalt feed liquid after the low sour back extractions of example 3., after the P204 removal of impurity, use the 25%(volume) the 5709-sulfonated kerosene is extracted organic phase, carries out five grades extraction, makes washings with 0.5N sulfuric acid, carries out Pyatyi and washs, extract and 50 ℃ of wash temperatures.Stream is than being water: have: wash=11.3: 6: 1.Extraction equipment is the centrifugal extractor of φ 20mm, the results are shown in Table three
Table three
The mineral acid back extraction of the organic phase of load cobalt, strip liquor are produced the high-purity cobalt metal again through deep purifying.
Claims (6)
1, with solvent extraction from the acidic solution separating and purifying Ni of nickel and cobalt containing and the method for cobalt, it is characterized in that carrying out multi-stage counter current extraction with a kind of organic phosphine extraction agent (domestic be called 5709) and said acidic solution, extraction temperature 35-60 ℃, the pH value 4.0-6.0 of extraction section outlet raffinate, raffinate is removed wherein organism through membrane phase degreasing unit, obtain the high purity nickel product by electrowinning with insoluble anode, cobalt-carrying solution after the back extraction obtains the high-purity cobalt product through 5709 extracting and purifyings again, and the structural formula of organic phosphine extraction agent (5709) is
R wherein
1Be the alkyl of 6-8 carbon atom, R
2Be 1-first heptyl.
2, in accordance with the method for claim 1, it is characterized in that the nickeliferous and cobalt liquor that said acidic solution leaches for the sulfuric acid selectivity.
3, according to the described method of claim 2., it is characterized in that the pH value of extraction section outlet raffinate is 4.0-6.0, best pH value is 4.5-5.0.
4,, it is characterized in that extraction temperature is 35-60 ℃, best extraction temperature 50-60 ℃ according to the described method of claim 2..
5, the extraction equipment that is used for claim 1. or 2. described methods is characterized in that this equipment is sieve diameter 3-6mm, is equilateral triangle and arranges, the free cross-section is 35%, the pulsed sieve-plate extraction column of distance between plates 50mm, pulse-response amplitude 12.5-15.0mm, pulse-repetition is 80-100 time/minute.
6, the oil removal plant that is used for claim 1 or 2 described methods is characterized in that this device is a membrane phase degreasing unit, and it comprises teeter column and phase separation chamber, is arranging sour mono alkyl ester in the phase separation chamber.Its structural formula is
R wherein
1Be the alkyl of 6-8 carbon atom,
R
2Be 1-first heptyl.
Extraction equipment can be used centrifugal extractor, mixer-settler or column extractor.As extraction equipment, its structural parameter and operational condition can be with pulsed sieve-plate column in the present invention: sieve diameter 3-6mm is equilateral triangle and arranges free cross-section 35%, distance between plates 50mm; Pulse-repetition 80-120 time/minute, pulse-response amplitude 12.5～15mm; Organic phase is as external phase.
Membrane phase degreasing unit is made up of teeter column and phase separation chamber, is arranging some phase membrane supports of dismounting separately that are surrounded by in the phase separation chamber.
The invention has the advantages that the selectivity acid leaching liquor extracts cobalt and other impurity of removing in the solution through a step, realizes the purification of electrolytic solution; The technology master operation adopts pulsed sieve-plate extraction column, and is simple in structure; Membrane phase degreasing unit is removed the organic matter efficiency height.In a word, technical process of the present invention is short, nickel cobalt yield height.
Fig. 1. be 5709 extracting and separating nickel cobalt purifying electrolysis effluograms.
Below in conjunction with Fig. 1. be described in detail implementing the present invention:
Sulphuric leachate is extracted agent (5709-kerosene) in extraction section (1) and carries out the Pyatyi counter-current extraction, and cobalt, copper, iron, lead, zinc etc. are extracted into organic phase in the leach liquor.Extraction temperature is 50-60 ℃, the pH value of leach liquor is 6.0-6.3, the saponification deg 30-50% of organic phase (5709), outlet water PH=4.5-5.0, whole pH value progressively descends from the first step to level V, can make the loss of extraction agent maintain minimum level and reduce acid and alkali consumption like this.Suitably reduce stream than (0/A), be surrounded by the phase membrane support of dismounting separately.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85105504A CN85105504B (en) | 1985-07-19 | 1985-07-19 | Method of separating and purifying ni and co with solvent extraction process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85105504A CN85105504B (en) | 1985-07-19 | 1985-07-19 | Method of separating and purifying ni and co with solvent extraction process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85105504A true CN85105504A (en) | 1987-03-04 |
| CN85105504B CN85105504B (en) | 1987-10-14 |
Family
ID=4794521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85105504A Expired CN85105504B (en) | 1985-07-19 | 1985-07-19 | Method of separating and purifying ni and co with solvent extraction process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85105504B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831547A (en) * | 2010-05-26 | 2010-09-15 | 江苏凯力克钴业股份有限公司 | Method for purifying cobalt solution |
| CN102859012A (en) * | 2010-03-18 | 2013-01-02 | 奥图泰有限公司 | Method of processing nickel bearing raw material |
| CN104099638A (en) * | 2013-04-07 | 2014-10-15 | 中国科学院过程工程研究所 | Method for removing metal ion impurity from nickel anode electrolyte |
-
1985
- 1985-07-19 CN CN85105504A patent/CN85105504B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102859012A (en) * | 2010-03-18 | 2013-01-02 | 奥图泰有限公司 | Method of processing nickel bearing raw material |
| CN102859012B (en) * | 2010-03-18 | 2015-11-25 | 奥图泰有限公司 | The method of process nickel-bearing raw material |
| CN101831547A (en) * | 2010-05-26 | 2010-09-15 | 江苏凯力克钴业股份有限公司 | Method for purifying cobalt solution |
| CN104099638A (en) * | 2013-04-07 | 2014-10-15 | 中国科学院过程工程研究所 | Method for removing metal ion impurity from nickel anode electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85105504B (en) | 1987-10-14 |
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